Colorphotographic material

ABSTRACT

IN WHICH R1 represents an alkyl radical; R2 represents an alkoxy radical, an alkylthio radical, a secondary or tertiary alkylamino group, a halogen, an alkyl radical, arylthio; R3 represents a substituent in the 4- or 5-position, which is: sulfonamide, carbamoyl, acylamino, an alkylsulfonyl; R4 represents hydrogen, an alkyl or alkoxy radical, halogen, sulfonamide or carbamoyl alkyl or alkylsulfonyl.   A light-sensitive photographic material containing in a silver halide emulsion layer a yellow coupler of the following formula:

United States Patent [72] Inventors Walter Schulte Opladen; HelmutMader, Leverkusen; Willibald Pelz, Opladen; Fritz Nittel, Cologne,Stammheim; Erich Reckziegel, Leverkusen,

all of Germany [21] Appl. No. 741,880

[22] Filed July 2, 1968 [45] Patented Oct. 26, 1971 [73] Assignee AFGAGevaert Aktiengesellschaft Leverkusen, Germany [32] Priority July- 10,1968 [33] Germany [54] COLORPHOTOGRAPHIC MATERIAL 9 Claims, No Drawings[52] US. Cl 96/100 [51] Int. Cl G03 1/40 [50] Field of Search 96/100[56] References Cited UNITED STATES PATENTS 3,393,040 7/1968 Verbruggheet al. 96/ 1 00 X FOREIGN PATENTS 1,039,965 8/1966 Great Britain 96/100Primary Examiner-Norman G. Torchin Assistant Examiner-John L. GoodrowAttorney-Connolly and Hutz ABSTRACT: A light-sensitive photographicmaterial containing in a silver halide emulsion layer a yellow couplerof the following formula:

R represents an alkoxy radical, an alkylthio radical, a secondary ortertiary alkylamino group, a halogen, an alkyl radical, arylthio;

R represents a substituent in the 4- or 5-position, which is:sulfonamide, carbamoyl, acylamino, an alkylsulfonyl;

R represents hydrogen, an alkyl or alkoxy radical, halogen, sulfonamideor carbamoyl alkyl or alkylsulfonyl.

color-forming developer. The resulting dye should, as far as possible,absorb only the desired spectral region since every side absorption inother spectral regions is disadvantageous. Furthermore, the resultingdyes should be light stable and stable even under the extreme conditionssuch as relatively high temperature and atmospheric moisture, found inthe tropics. The color couplers themselves which are incorporated in thelight-sensitive layer, should, also, of course possess sufficientstability under tropical conditions. The yellow couplers hitherto knowndo not meet requirements in practice in particular with regard to thelast mentioned property. Furthermore, for economical reasons, only thosecolor couplers which can be prepared by a simple method are of interest.

An object of this invention is to provide couplers which, are stableunder tropical conditions and to light, and which can be produced inhigh yields and in pure form. We now have found that compounds ofbenzoyl acetanilide type of the following formula are especiallysuitable for use as yellow couplers in photographic silver halideemulsion layers:

R2 A-NH-C ooH,-o o O-R1 l L 5 6 soar in which R represents an alkylradical preferably containing one to 18 carbon atoms;

R represents 1. an alkoxy radical preferably containing up to 18 carbonatoms;

2. an alkylthio radical preferably containing up to 18 carbon atoms;

3. a secondary or tertiary alkylamino group preferably containing up to18 carbon atoms or a preferably saturated fiveor six-memberednitrogen-containing heterocyclic ring such as pyrrolidine or piperidinelinked to the benzene nucleus through the nitrogen atom;

4. a halogen atom such as chlorine or bromine or an alkyl radical; thealkyl groups of the above substituents may contain further substituents,e.g. halogen atoms, to form in particular, a trifluoromethyl group, orphenyl radicals;

6. Arylthio preferably phenylthio particularly alkyl substituted phenyl,halogensubstituted phenyl;

7. Aroxy preferably phenoxy particularly alkyl substituted phenyl,halogen substituted phenyl 8. Aralkoxy preferably benzyloxy orsubstituted benzyloxy such as halogen substituted or alkyl sub stitutedbenzyloxy;

R represents a substituent in the fouror five-position,

preferably in the five-position, which is:

l. sulfonamide in which the amide group may be substituted by alkylradicals which preferably contain one to 18 carbon atoms;

2. carbamoyl in which the amide group may be substituted by alkylradicals which have preferably one to 18 carbon atoms;

3. acylamino, acylamino,-preferably monoacylamino, in which the acylgroups are preferably derived from aliphatic carboxylic or sulfonicacids which have up to 18 carbon atoms, or

4. a alkylsulfonyl which preferably contains up to 18 carbon atoms;

R represents hydrogen, an alkyl or alkoxy radical preferably containingup to five carbon atoms, halogen such as chlorine or bromine,sulfonamide or carbamoyl in which the amide groups may be substituted byalkyl radicals which preferably contain up to 18 carbon atoms oralkylsulfonyl, preferably containing up to l8 carbon atoms.

In the above general formula, the benzene rings, especially the benzenering present in the amide part of the color coupler molecule, maycontain any other substituents in addition to those already mentioned,e.g., alkyl or alkoxy groups, or halogen atoms.

Examples of suitable color couplers are shown in the following table:

| SOaH benzene ring of the amide part of the molecule so that sulfona-COUPLER l 3-Nitro-4-methoxybenzesulfonie acid-N-stearyl amide 81 g. ofstearylamine and 40 ml. of triethylamine are dissolved in 800 ml. oftetrahydrofuran. A solution of 75 g. of 3nitro-4-methoxybenzenesulfochloride in 200 ml. of tetrahydrofuran are addeddropwise with stirring and the reaction mixture is stirred for 1 hour atroom temperature. The mixture is stirred into a mixture of ice andwater, suction filtered and recrystallized from dioxane.

Yield: 140 g., m.p. 102 C.

3-Amino-4-methoxybenzenesulfonic acid-N-stearyl amide 130 g. of theabove nitro compound are hydrogenated in 1,600 ml. of methanol at '50atmospheres and 50 C. with Raney nickel. The product is filtered whilehot and cooled to C. The precipitated amine is suction filtered, washedwith methanol and dried in air. Yield: 100 g., m.p. 89 C.

34 g. of the above amine are heated to 140 C. in 25 ml. of triethylamineand 300 ml. of chlorobenzene, and a solution of 25 g. of the acetic acidethyl ester in 100 ml. of chlorobenzene is added dropwise with stirring,The reaction mixture is refluxed for 4 hours. It is then cooled to 0 C.and the product is precipitated with methanol. After suction filtrationand washing with methanol, the product ,is recrystallized from alcohol.

Yield: 58 g. m.p. 140 C.

38 g. of the product are slowly introduced into 230 ml.of sulfuric acidmonohydrate at room temperature. The reaction mixture is stirred forabout 1 hour and heated to40 C. until a sample precipitated with ice isnot soluble in alkali. The mixture is then stirred into ice and theprecipitated coupler is suction filtered, washed with 'witer'ina'recrystallized from methanol.

Yield: 28 g., m.p. l30l40C. with decomposition.

COUPLER 4 3-Nitro-4-chlorobenzenesulfone-N-methyl-N-stearyl amide 136 g.of methylstearylamine are dissolved in 700 ml. of tetrahydrofuran and asolution of 128 g. of 4-chlor-3- nitrobenzenesulfochloride in 300 ml. oftetrahydrofuran is added dropwise, The reaction mixture is stirred for30 minutes and then poured into 2 liters of iced water. The productwhich precipitates out is suction filtered and recystallized fromalcohol. Yield: 138 g.,m.p. 89C.

3-Nitro-4-methylbenzylamino-N-methyl-N-stearylbenezene-sulfonamide, 260g. of the above product and 144 g. of methylbenzylamine are refluxed for6 hours in 400 ml. of

-isopropanol. The precipitated product is suction filtered,

washed with H 0 and recrystallized from methanol. Yield: 178 g., m.p.l30 C.

REDUCTION 180 g. of the above compound in 2 l. of ethanol arehydrogenated in the presence of Raney nickel at 50 C. and 50 atmospherespressure. The catalyst is removed by filtration under suction, thesolution is cooled to 0 C. and the precipitated product is suctionfiltered and washed with ethanol.

Yield: 130 g., m.p. 55-57 C.

A mixture of 33 g. or 4-methoxybenzoyl acetic acid ethyl ester and 200ml. of chlorobenzene are added dropwise to a solution of 56 g. of theabove product and 30 ml. of triethylamine in 300 ml. of chlorobenzene atC. The reactions mixture is then heated for 4 hours at 140 C. withstirring, during which time a small amount of chlorobenzene and alcoholdistil off. The mixture is then concentrated by evaporation under vacuumand the residue is recrystallized from ethanol.

Yield: 62 g., m.p. 4344 C.

30 g. of the product are added slowly to 180 ml. of sulfuric acidmonohydrate. The reaction mixture is then stirred for one hour at 30 to35 C. and poured onto ice. The precipitated product is suction filtered.After it has been washed with water, it is recrystallized from methanol.

Yield: 20 g.

The other couplers may be prepared in analogous manner.

The color couplers to be used in accordance with the present inventionare incorporated in the silver halide emulsion by known methods. Theyare preferably added before casting in the form of a solution, e.g. inthe form of a solution, e.g. in the form of a solution of their alkalimetal salts, to the blue-sensitive silver halide emulsion.

According to another known method, solutions of the color couplers whichare hydrophobic, may be emulsified if desired in the presence ofso-called oil formers, in gelatin, after which the resulting emulsion isdried, and allowed to swell again in water and is then mixed with thesilver halide gelatin emulsion. Other processes are known according towhich the solution of the color coupler in an organic solvent is mixeddirectly with the silver halide emulsion, and the silvent is evaporatedoff. The color couplers according to the invention may be used in any ofthese processes. The binders which may be used for the layers are theknown hydrophilic film-forming agents such as proteins, especiallygelatin, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivativessuch as carboxyalkyl-cellulose, especially carboxamethylcellulose,derivatives of alginic acid and their alkali metal salts or esters.

The layers may in addition be stabilized by known additives, inparticular the azaindene derivatives described in the publication byBirr in Z. wiss. Phot. 47 [952), pages 2-28.

' The layer support is transparent or opaque depending on the purposefor which the light-sensitive material is to be used and maybe made ofpaper, glass, cellulose esters such as cellulose nitrate or cellulosetriacetate, polyesters, polystyrene or other high molecular weightnatural or synthetic materials.

The yellow couplers according to the invention are usually incorporatedwith the light-sensitive layer itself. In addition, they may also beadded to a layer which is not light sensitive and which is in contactwith the blue-sensitized layer, or with a layer of colloid which isseparated from the blue-sensitized layer by a water-permeable layer ofcolloid.

The yellow couplers of the present invention can be applied forcolorphotographic materials to be used for a negative-positive processas well as for a colorphotographic reversal process.

Any color-forming developers which contain a primary amino group may beused for the development step. Those of the p-phenylenediamine type,e.g. N,N-diethyl-p-phenylenediamine, monomethyl-p-phenylenediamine,N,N'- dimethyl-p-phenylenediamine, Z-amino-S- diethylaminotoluene andN-butyl-Nw-sulfobutyl-p-phenylenediamine are preferred.

EXAMPLE 1 4 mols of coupler 8 are dissolved in water containing a smallamount of alcohol and sodium hydroxide solution. The total volume of thesolution is about 100 ml. and the pH should range between 7 and 9. Thecoupler solution prepared in this way is added to 50 ml. of aphotographic silver bromide gelatine emulsion which contains 7 percentof gelatin and 0.5 mol of silver bromide per kg. of emulsion. ml. of 7.5percent gelatin solution, 5 ml. of a 1 percent methanolic solution f 4.hd .6 h l l3 3 7- i d 6 l of R an alkylsulfamyl group containing up tofour carbon aqueous saponin solution (l percent) and 3 ml. of aqueousatoms chrome acetate solution (0.5 percent) are added to this cou- 2.Light-sensitive photographic material as defined in claimpler-containing emulsion which is then cast on a support of wherein is mhy cellulose triacetate to form a layer about 5 p. in thickness. The 5 ge e photographic material as defined in claim pH of the layer is about6.5-7 percent. 1 wherein 3 is a Sulfonamide p- After dryin th materi l ix o ed th gh a grey t 4. Light-sensitive photographic material asdefined in claim wedge and developed for 8 minutes in a developersolution of 2 wherein 3 is a monomethylsulfonamide g pthe followingcomposition. 1 0 5. Light-sensitive photographic material as defined inclaim 2.75 g. of N,N-diethyl-p-phenylenediaminosulfate, l whe rein Rstands for alkoxy containing up to 1 8 carbon 1.2 g. ofhydroxylaminohydrochloride, atoms or a tertiary alkyl amino group, thealkyl radicals of 2 g, of anhydrou N $0 which contain up to 18 carbonatoms. 2 g. of sodium metaphosphate, 6. Light-sensitive photographicmaterial as defined in claim 75 g. of potassium carbonate, 1 5 2 inwhich the color couplerhas the following formula: 2 g. of potassiumbromide and water up to l 1. Further processing includes treatment inthe following CH3 CHE baths:

N BLEACHING BATH NH-c-cm-c-ocm 3 g. of ethylenediaminotetracetic acid, Hll 50 g. of potassium ferricyanide, 0 O 0 H g. of potassium bromide, lg. of disodium phosphate, Q2NH CH3 19 g. of monopotassium phosphate,water up to l l. 2 The fixing bath consists of a solution of 200 g. ofsodium thiosulfate in 1 1. ofwaten 7. Light-sensitive photographicmaterial as defined in claim The processing times after development areas follows: 3 in which the color coupler has the 8 formula: 15 minuteswashing 5 minutes bleaching bath v "Has 5 minutes washing 5 minutesfixing bath NH C CHT C O 0H, 10 minutes washing. I I] I] A yellow imageof the step wedge is obtained. 0 0 g 11 If the yellow image is exposedto 96 percent relative humidity for one day at 60 C., no reduction isfound at a density of I 0.5 and 1.5.

- 8. Light-sensitive photographic material as defined in claim EXAMPLE 23 in which the color coupler has the following formula: The sameprocedure is employed as carried out in example 1 except that thecoupler used in coupler 4. A yellow image OCH: with maximum density 2.6and gradation 3.4 is obtained.

When the film is stored under the conditions used in exam- HFC ple 1, noreduction 15 found at dens ty and l g I;

We claim: 0 N u 80 1i 1. Light-sensitive photographic materialcomprising at least I one silver halide emulsion layer which contains ayellow cou- CH3 pler of the following formula:

R2 9. Light-sensitive photographic material as defined in claim I 2, inwhich the color coupler has the following fonnula:

l Ra SOaH N wherein: I

R, methyl; NHC-C H;C'OCH: R I

1 an alkoxy radical containing up to 18 carbon atoms; or 30:11 2 asecondary or tertiary alkylamino group containing up I to 18 carbonatoms is one of the alkyl residues; and z 4 v UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 615,606 DATEDOctober 26, 1971 INVENTOMS) WALTER SCHULTE et al It is certified thaterror appears in the above-identified patent and that said LettersPatent is hereby corrected asshown below: on the title page Column 1, inthe Priority date, cancel "1968" and insert 1967 The Priority date lineshould read as follows:

[32] Priority July 10, 1967.

Column 9, line 61, cancel "is" and insert in Column 6, line 67, cancel"acetate" and insert acetic acid esters line 67 should read as follows:

"benzoyl acetic acid ester in the presence of a suitable base such as"Same column, line 68 cancel "acetic acid ester" and insert sodiumacetate line 68, should read as follows "triethylamine, pyridine orsodium acetate".

Column 7, line 33, before "acetic" insert p-methoxybenzoyl and line 33should read as follows:

"25q. of the p-methoxybenzoyl acetic acid ethyl ester in 100 ml.

of chlorobenzene.

Signed and Scaled this Twenty-ninth D a y f March I 983 |SAL| Armc-GERALD J. MOSSINGI'IOFF Arresting Officer Commissioner of Parents andTrademarks

2. Light-sensitive photographic material as defined in claim 1, whereinR1 is methyl.
 3. Light-sensitive photographic material as defined inclaim 1 wherein R3 is a sulfonamide group.
 4. Light-sensitivephotographic material as defined in claim 2 wherein R3 is amonomethylsulfonamide group.
 5. Light-sensitive photographic material asdefined in claim 1 wherein R2 stands for alkoxy containing up to 18carbon atoms or a tertiary alkyl amino group, the alkyl radicals ofwhich contain up to 18 carbon atoms.
 6. Light-sensitive photographicmaterial as defined in claim 2 in which the color coupler has thefollowing formula:
 7. Light-sensitive photographic material as definedin claim 3 in which the color coupler has the following formula: 8.Light-sensitive photographic material as defined in claim 3 in which thecolor coupler has the following formula:
 9. Light-sensitive photographicmaterial as defined in claim 2, in which the color coupler has thefollowing formula: